Is there a way to limit the 'from email address' in the personal preferences? I'm able to set this value with the 'N/Config' module, though it seems a bit retrospective.

What do you mean by “limit”?

is there any options to restrict this field? ideally disable the field entirely or have certain roles unable to enter values

I haven’t found a way to customise/script the Preferences page but perhaps others know a way

best i've got is adding a UE event on viewing transactions which check the preferences fields then remove or change the value if criteria is met